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Title: Surface degradation of Li{sub 1–x}Ni{sub 0.80}Co{sub 0.15}Al{sub 0.05}O{sub 2} cathodes: Correlating charge transfer impedance with surface phase transformations

Abstract

The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1 V (versus Li/Li{sup +}) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li{sub 1–x}Ni{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2} binder-free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and 4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of significant Li{sub 2}CO{sub 3} and LiF. These data provide evidence that surface oxygen loss at the highest levels of Li{sup +} extraction is driving the rise in impedance.

Authors:
 [1]; ; ;  [2]; ;  [3];  [4]; ;  [5];  [6];  [1];  [7]
  1. Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States)
  2. Energy Storage Research Group, Department of Materials Science and Engineering, Rutgers University, North Brunswick, New Jersey 08902 (United States)
  3. Department of Materials Science and Engineering, Rutgers University, North Brunswick, New Jersey 08902 (United States)
  4. Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902 (United States)
  5. Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE (United Kingdom)
  6. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
  7. (United States)
Publication Date:
OSTI Identifier:
22590666
Resource Type:
Journal Article
Resource Relation:
Journal Name: Applied Physics Letters; Journal Volume: 108; Journal Issue: 26; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; CATHODES; CATIONS; ELECTRIC POTENTIAL; ELECTROCHEMISTRY; ELECTROLYTES; ELECTRON MICROSCOPY; LITHIUM CARBONATES; LITHIUM FLUORIDES; LITHIUM ION BATTERIES; LITHIUM IONS; OXIDES; PHASE TRANSFORMATIONS; SURFACES; X-RAY SPECTROSCOPY

Citation Formats

Sallis, S., Pereira, N., Faenza, N., Amatucci, G. G., Mukherjee, P., Cosandey, F., Quackenbush, N. F., Schlueter, C., Lee, T.-L., Yang, W. L., Piper, L. F. J., E-mail: lpiper@binghamton.edu, and Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902. Surface degradation of Li{sub 1–x}Ni{sub 0.80}Co{sub 0.15}Al{sub 0.05}O{sub 2} cathodes: Correlating charge transfer impedance with surface phase transformations. United States: N. p., 2016. Web. doi:10.1063/1.4954800.
Sallis, S., Pereira, N., Faenza, N., Amatucci, G. G., Mukherjee, P., Cosandey, F., Quackenbush, N. F., Schlueter, C., Lee, T.-L., Yang, W. L., Piper, L. F. J., E-mail: lpiper@binghamton.edu, & Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902. Surface degradation of Li{sub 1–x}Ni{sub 0.80}Co{sub 0.15}Al{sub 0.05}O{sub 2} cathodes: Correlating charge transfer impedance with surface phase transformations. United States. doi:10.1063/1.4954800.
Sallis, S., Pereira, N., Faenza, N., Amatucci, G. G., Mukherjee, P., Cosandey, F., Quackenbush, N. F., Schlueter, C., Lee, T.-L., Yang, W. L., Piper, L. F. J., E-mail: lpiper@binghamton.edu, and Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902. 2016. "Surface degradation of Li{sub 1–x}Ni{sub 0.80}Co{sub 0.15}Al{sub 0.05}O{sub 2} cathodes: Correlating charge transfer impedance with surface phase transformations". United States. doi:10.1063/1.4954800.
@article{osti_22590666,
title = {Surface degradation of Li{sub 1–x}Ni{sub 0.80}Co{sub 0.15}Al{sub 0.05}O{sub 2} cathodes: Correlating charge transfer impedance with surface phase transformations},
author = {Sallis, S. and Pereira, N. and Faenza, N. and Amatucci, G. G. and Mukherjee, P. and Cosandey, F. and Quackenbush, N. F. and Schlueter, C. and Lee, T.-L. and Yang, W. L. and Piper, L. F. J., E-mail: lpiper@binghamton.edu and Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902},
abstractNote = {The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1 V (versus Li/Li{sup +}) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li{sub 1–x}Ni{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2} binder-free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and 4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of significant Li{sub 2}CO{sub 3} and LiF. These data provide evidence that surface oxygen loss at the highest levels of Li{sup +} extraction is driving the rise in impedance.},
doi = {10.1063/1.4954800},
journal = {Applied Physics Letters},
number = 26,
volume = 108,
place = {United States},
year = 2016,
month = 6
}